CN104419439B - A kind of direct coal liquefaction process of two-stage hydrogenation - Google Patents
A kind of direct coal liquefaction process of two-stage hydrogenation Download PDFInfo
- Publication number
- CN104419439B CN104419439B CN201310385008.XA CN201310385008A CN104419439B CN 104419439 B CN104419439 B CN 104419439B CN 201310385008 A CN201310385008 A CN 201310385008A CN 104419439 B CN104419439 B CN 104419439B
- Authority
- CN
- China
- Prior art keywords
- reactor
- hydrogen
- reaction
- coal
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the direct coal liquefaction process of a kind of two-stage hydrogenation, the coal slurry, hydrogen and the catalyst that are mixed into hydrogen supply solvent including coal dust react in A reactor, reaction temperature is 420 460 DEG C, first order reaction product is sent into the top of second reactor, gaseous component in first order reaction product is flowed out by second reactor top, solid-liquid component flows downward in second reactor, react with the hydrogen counter current contacting flowed up, reaction temperature is 430 480 DEG C, and reaction separates product after terminating.The gas holdup being not involved in reacting gas in second reactor can be reduced to less than 15% by this technique, significantly improves the production efficiency of DCL/Direct coal liquefaction.It is applicable to extensive DCL/Direct coal liquefaction industry.
Description
Technical field
The present invention relates to the direct coal liquefaction process of a kind of two-stage hydrogenation, belong to direct coal liquefaction technology field.
Background technology
DCL/Direct coal liquefaction is the technology making coal catalytic hydrogenation at high temperature under high pressure be converted into liquid fuel, at present
The most successfully have developed multiple direct coal liquefaction process, including Germany IGOR technique, U.S. H-Coal
Technique, Japan's NEDOL technique and Shenhua of China technique.Wherein, Shenhua of China technique was built up in 2008
The industrial demonstration unit of 6000 ton day has also put into use.
Being found by long-term research, first coal experiences in direct liquefaction before fast pyrogenation reaction generates in a large number and drips
Blue or green alkene, asphaltene and some small molecule hydrocarbons, CO2, the gas such as CO, preasphaltene the most therein and Colophonium
Alkene may proceed to be hydrogenated with and is cracked into small molecule hydrocarbon and gas further.But, due to coal fast pyrogenation react be with
Radical reaction is main, and the free radical fragment that pyrolysis produces the most mutually collides and aggregates into macromole coke, therefore
DCL/Direct coal liquefaction point two-stage is typically carried out by prior art, uses relatively low pyrolysis in one-level fast pyrogenation reacts
Temperature controls the generating rate of free radical, mixes proper amount of reactive hydrogen simultaneously and eliminates the free radical of generation in time
Fragment.As Chinese patent literature CN102115674A discloses the combined method of a kind of coal liquefaction and petroleum refining,
Step is 1) by petroleum distillate I, product liquid fraction I and catalyst that coal dust and boiling range are 150-343 DEG C
Being mixed into coal slurry, in coal slurry, the solid content of coal is 10-50%;2) coal slurry is entered one by bottom together with hydrogen
Stage reactor, carries out pyrolysis of coal hydrogenation reaction at 360-450 DEG C;3) A reactor effluent, boiling range are
The petroleum distillate II of 343-600 DEG C and product liquid fraction II mix and are entered second reactor by bottom,
Hydrocracking reaction is carried out at 420-480 DEG C;4) second reactor effluent is isolated to gas, liquid produces
Thing fraction I, product liquid fraction II and residue, partial liquid product fraction I loops back in A reactor,
Partial liquid product fraction II loops back in second reactor.
Although above-mentioned technology can effectively reduce the collision polymerization probability between the free radical that coal fast pyrogenation produces, subtract
The generation of few coke, but the production efficiency of above-mentioned direct coal liquefaction process is the lowest, and those skilled in the art are always
Can not find the reason causing above-mentioned production efficiency low.
Further, control the carrying out of reaction for convenience, the two-stage hydrogenation direct coal liquefaction process of prior art is all
Raw material and hydrogen are sent into by bottom A reactor, then by first order reaction product and hydrogen by second reactor
Bottom is sent into, and makes the gas-solid material following current hybrid reaction in one-level or second reactor.Although introducing secondary response
Containing a certain amount of small molecule hydrocarbon being not involved in reaction and CO, CO in first order reaction product in device2Deng gas,
But prior art generally believing, this part is only not involved in the gas of reaction gas holdup in the second reactor
For 10-15%, do not interfere with the carrying out of reaction.
Summary of the invention
The technical problem to be solved is that the two-stage hydrogenation direct coal liquefaction process of prior art produces effect
Rate is the lowest, and those skilled in the art can not find the reason that this production efficiency is low always;And then propose one
Plant the two-stage hydrogenation direct coal liquefaction process that production efficiency is high.
For solving above-mentioned technical problem, the invention provides the direct coal liquefaction process of a kind of two-stage hydrogenation, including
Following steps,
(1) coal dust and hydrogen supply solvent being mixed into coal slurry, described coal slurry, hydrogen and catalyst are anti-in one-level
Answering reaction in device, reaction temperature is 420-460 DEG C, and reaction end obtains first order reaction product;
(2) described first order reaction product is sent into the top of second reactor, in described first order reaction product
Gaseous component is flowed out by second reactor top, and solid-liquid component flows downward in described second reactor, with institute
The hydrogen counter current contacting reaction flowed up in stating second reactor, reaction temperature is 430-480 DEG C, reaction knot
Secondary response product is obtained after bundle;
(3) by the solid-liquid Component seperation in described secondary response product.
In described second reactor, the flow velocity that described solid-liquid component flows downward is 1-10cm/s.
Hydrogen-oil ratio 600-1000 in described second reactor.
Hydrogen dividing potential drop in described second reactor is 10-15MPa.
Reaction pressure in described second reactor is 15-20MPa.
In described A reactor, reaction pressure is 15-20MPa, and hydrogen dividing potential drop is 10-15MPa.
The coal dust content of described coal slurry is 30-50wt%, and the weight of described catalyst is the 0.1 of described coal dust weight
-10.0%。
Described coal dust is one or both in bituminous coal and ub-bituminous coal, described hydrogen supply solvent be heavy oil, residual oil and
The mixture of one or more in liquid distillate in step (3).
In step (1), after described coal slurry, catalyst and hydrogen are mixed, pressurize and heat, send bottom
Enter in described A reactor.
Gaseous component in described secondary response product mixes laggard with the gaseous component in first order reaction product mutually
Row separates, and isolated hydrogen-rich gas uses as the hydrogen in step (1) and (2).
The present invention has the advantages that compared with prior art
(1) two-stage of the present invention hydrogenation direct coal liquefaction process, comprise the steps 1) by coal dust with
Hydrogen supply solvent is mixed into coal slurry, and described coal slurry, hydrogen and catalyst react in A reactor, reaction temperature
Degree is for 420-460 DEG C, and reaction end obtains first order reaction product;2) described first order reaction product is sent into two grades
The top of reactor, the gaseous component in described first order reaction product is flowed out by second reactor top, solid-liquid group
Point flow downward in described second reactor, with the hydrogen counter current contacting that flows up in described second reactor
Reaction, reaction temperature is 430-480 DEG C, and reaction obtains secondary response product after terminating;3) by described two grades anti-
The solid-liquid component in product is answered to carry out separating.
When prior art being thought by first order reaction product introducing second reactor, first order reaction product is not involved in
The small molecule hydrocarbon of reaction and CO, CO2It is only 10-15%, not shadow Deng gas gas holdup in second reactor
Ring the carrying out of secondary response, therefore prior art will not be gone to get rid of the gas being not involved in reaction in first order reaction thing,
To simplify production technology, to reduce production cost.And, carry out, in prior art all for ease of controlling reaction
It is that first order reaction product and hydrogen are introduced by the bottom of second reactor, makes gas-solid material carry out following current mixing anti-
Should.But, the application applicant finds to be not involved in reaction in first order reaction product after a large amount of creative researches
Small molecule hydrocarbon and CO, CO2It is up to 40% Deng gas gas holdup in second reactor is actual, the most notable
Decrease the effective reaction space in second reactor the mass transfer hindering between reactant, thus result in two grades instead
Answer the hydrocracking reaction efficiency in device substantially to reduce, cause the production efficiency of direct coal liquefaction process to reduce;Base
In above-mentioned discovery, coal, on the premise of the most additionally increase equipment, is first carried out fast at 420-460 DEG C by applicant
Speed pyrolytic reaction, and add a certain amount of hydrogen supply solvent and be diluted, to reduce between produced free radical
Collision polymerization, reduces the generation of coke, then the first order reaction product generated is sent into second reactor top,
The reaction temperature simultaneously keeping second reactor is 430-480 DEG C, with this understanding, arrives on second reactor
Gaseous component in the first order reaction product in portion can be flowed out by reactor head, and solid liquid phase component can flow downward also
Cracking reaction is carried out with the hydrogen flowed up counter current contacting in reactor, can be one-level by counter current contacting
Product does not continue to participate in the gas of the reaction gas holdup in second reactor and is reduced to less than 15%, with
The utilization rate in space in raising second reactor, the product generated is fractionated into refining and i.e. obtains Coal Liquefaction Products.
First order reaction product is processed by this technique without being further provided with equipment, reacts at above-mentioned process conditions next stage
After product enters second reactor top, product is not involved in the gaseous component of secondary response i.e. by reactor head
Flow out, take the useful space in second reactor, so that second reactor had both played cracking reaction to reduce
The effect of device, play again gas separate effect, and in separation process in first order reaction product original greatly
Partial heat is brought into second reactor and is continuing with, saved energy, it is to avoid two-stage hydrogenation in prior art
The production efficiency of direct coal liquefaction process is low, the problem that those skilled in the art cannot improve its production efficiency always.
And, use the above-mentioned technique to be separated in time by the gaseous light hydrocarbons generated in A reactor, it is to avoid this portion
Divide lighter hydrocarbons problem of transition cracking in second reactor, improve the yield of light hydrocarbon product.
(2) direct coal liquefaction process of two-stage of the present invention hydrogenation, in described second reactor, described solid
The flow velocity that liquid component flows downward is 1-10cm/s.In above-mentioned technique, by downward for solid-liquid component in second reactor
The flow speed control of flowing within the specific limits, makes solid-liquid component can more fully carry out counter current contacting with hydrogen, improves
The yield of reaction;Meanwhile, speed controlling solid-liquid component flowed downward is within the specific limits, it is possible to reduce stream
Dynamic solid-liquid component is entrained into gaseous component, thus further reduces gaseous component to effective in second reactor
Taking of space, improves the yield of liquiefied product.
(3) direct coal liquefaction process of two-stage of the present invention hydrogenation, the hydrogen-oil ratio in described second reactor
600-1000.Hydrogen dividing potential drop in described second reactor is 10-15MPa.Reaction in described second reactor
Pressure is 15-20MPa.Carry out secondary hydrogenation reaction under this condition, first order reaction product can be reduced further
In be not involved in the gaseous component of reaction the useful space in second reactor taken, promote in second reactor one
Order reaction product and the counter current contacting of hydrogen, thus improve the production of two-stage hydrogenation direct coal liquefaction process further
Efficiency and the yield of final liquiefied product.
Detailed description of the invention
The technology contents of the present invention is expanded on further below in conjunction with embodiment.
Embodiment 1
(1) pulverized bituminous coal and heavy oil are mixed to form the coal slurry that coal dust content is 30wt%, mix in coal slurry
React together send into the A reactor of 10L after the iron sulfide catalyst of 0.03wt% with hydrogen in, reaction pressure
For 15MPa, hydrogen dividing potential drop is 10MPa, and reaction temperature is 420 DEG C, and air speed is 0.25h-1, reaction end obtains
First order reaction product;
(2) described first order reaction product is sent into the top of the second reactor of 8L, and described first order reaction is produced
Gaseous component in thing is flowed out by second reactor top, and the solid-liquid component in first order reaction product flows downward,
Flow speed control is that the hydrogen counter current contacting flowed up in 1-5cm/s, with described second reactor is reacted, hydrogen oil
Ratio is 600, and reaction pressure is 15MPa, and hydrogen dividing potential drop is 10MPa, and reaction temperature is 430 DEG C, and air speed is 0.25h-1,
Reaction obtains secondary response product after terminating;
(3) after the liquid in described secondary response product, solid Component seperation, liquid distillate and residue are obtained;Will
Gaseous component in described secondary response product carries out cold after mixing mutually with the gaseous component in first order reaction product
Solidifying separation, obtains gas and light distillate.
Embodiment 2
(1) pulverized bituminous coal of weight ratio 1:1 and anthracite coal dust are mixed to form total coal dust content with residual oil and are
The coal slurry of 50wt%, mixes the ZnCl of 5wt% in coal slurry2/ S catalyst (wherein ZnCl2For active component,
S is auxiliary agent, and the atomic ratio of S, Zn is 0.5) together send into the A reactor of 10L afterwards with hydrogen in react,
Reaction pressure is 20MPa, and hydrogen dividing potential drop is 15MPa, and reaction temperature is 460 DEG C, and air speed is 0.25h-1, reaction
Terminate to obtain first order reaction product;
(2) described first order reaction product is sent into the top of the second reactor of 8L, and described first order reaction is produced
Gaseous component in thing is flowed out by second reactor top, and the solid-liquid component in first order reaction product flows downward,
Flow speed control is that the hydrogen counter current contacting flowed up in 6-10cm/s, with described second reactor is reacted, hydrogen oil
Ratio is 1000, and reaction pressure is 20MPa, and hydrogen dividing potential drop is 15MPa, and reaction temperature is 480 DEG C, and air speed is
0.25h-1, reaction obtains secondary response product after terminating;
(3) after the liquid in described secondary response product, solid Component seperation, liquid distillate and residue are obtained;Will
Gaseous component in described secondary response product carries out cold after mixing mutually with the gaseous component in first order reaction product
Solidifying separation, obtains gas and light distillate.
Embodiment 3
(1) ub-bituminous coal coal dust, the heavy oil of weight ratio 1:1 are mixed to form coal dust content mutually with the mixture of residual oil
For the coal slurry of 40wt%, in coal slurry, mix ferrum molybdenum catalyst (the wherein atomic ratio of ferrum, molybdenum of 2wt%
Be 50) together send into the A reactor of 10L afterwards with hydrogen in react, reaction pressure is 18MPa, and hydrogen divides
Pressure is 14MPa, and reaction temperature is 440 DEG C, and air speed is 0.25h-1, reaction end obtains first order reaction product;
(2) described first order reaction product is sent into the top of the second reactor of 8L, and described first order reaction is produced
Gaseous component in thing is flowed out by second reactor top, and the solid-liquid component in first order reaction product flows downward,
Flow speed control is that the hydrogen counter current contacting flowed up in 3-7cm/s, with described second reactor is reacted, hydrogen oil
Ratio is 800, and reaction pressure is 18MPa, and hydrogen dividing potential drop is 14MPa, and reaction temperature is 450 DEG C, and air speed is 0.25h-1,
Reaction obtains secondary response product after terminating;
(3) after the liquid in described secondary response product, solid Component seperation, liquid distillate and residue are obtained;Will
Gaseous component in described secondary response product carries out cold after mixing mutually with the gaseous component in first order reaction product
Solidifying separation, obtains gas and light distillate.
Embodiment 4
(1) by pulverized bituminous coal, weight ratio 2:1 heavy oil with > liquid distillate of 350 DEG C is mixed to form coal dust mutually
Content is the coal slurry of 30wt%, with hydrogen together sends into after mixing the iron sulfide catalyst of 5wt% in coal slurry
Reaction in the A reactor of 10L, reaction pressure is 15MPa, and hydrogen dividing potential drop is 14MPa, and reaction temperature is
435 DEG C, air speed is 0.25h-1, reaction end obtains first order reaction product;
(2) described first order reaction product is sent into the top of the second reactor of 8L, and described first order reaction is produced
Gaseous component in thing is flowed out by second reactor top, and the solid-liquid component in first order reaction product flows downward,
Flow speed control is that the hydrogen counter current contacting flowed up in 1-10cm/s, with described second reactor is reacted, hydrogen oil
Ratio is 700, and reaction pressure is 15MPa, and bottom hydrogen dividing potential drop is 15MPa, and reaction temperature is 470 DEG C, air speed
For 0.25h-1, reaction obtains secondary response product after terminating;
(3) after the liquid in described secondary response product, solid Component seperation, liquid distillate and residue are obtained;Will
Gaseous component in described secondary response product is carried out after mixing mutually with the gaseous component in first order reaction product point
From, obtain gas and light distillate;Wherein, the hydrogen-rich gas obtained can reuse anti-to A reactor and two grades
Answer in device and use as hydrogen, > liquid distillate of 350 DEG C can be mixed with first order reaction with heavy oil, pulverized bituminous coal
The coal slurry raw material that device uses.
Embodiment 5
(1) ub-bituminous coal coal dust with > liquid distillate of 350 DEG C is mixed to form the coal slurry that coal dust content is 45wt%,
React together send into the A reactor of 10L after mixing the iron sulfide catalyst of 5wt% in coal slurry with hydrogen in,
Reaction pressure is 20MPa, and hydrogen dividing potential drop is 18MPa, and reaction temperature is 430 DEG C, and air speed is 0.25h-1, reaction
Terminate to obtain first order reaction product;
(2) described first order reaction product is sent into the top of the second reactor of 8L, and described first order reaction is produced
Gaseous component in thing is flowed out by second reactor top, and the solid-liquid component in first order reaction product flows downward,
Flow speed control is that the hydrogen counter current contacting flowed up in 1-10cm/s, with described second reactor is reacted, hydrogen oil
Ratio is 1000, and reaction pressure is 20MPa, and bottom hydrogen dividing potential drop is 15MPa, and reaction temperature is 480 DEG C, empty
Speed is 0.25h-1, reaction obtains secondary response product after terminating;
(3) after the solid-liquid component fractionation in described secondary response product, liquid distillate and residue are obtained;By institute
State after the gaseous component in secondary response product mixes mutually with the gaseous component in first order reaction product and separate,
Obtain gas products and light distillate, wherein, > liquid distillate of 350 DEG C can be mixed with mutually with ub-bituminous coal coal dust
The coal slurry raw material that A reactor uses.
Embodiment 6
(1) miscella that heavy oil and residual oil are formed with 1:1 weight ratio is mixed into coal dust content with pulverized bituminous coal and is
The coal slurry of 40wt%, together sends into the one of 10L in coal slurry with hydrogen after mixing the iron sulfide catalyst of 5wt%
Reaction in stage reactor, reaction pressure is 17MPa, and hydrogen dividing potential drop is 15MPa, and reaction temperature is 400 DEG C, empty
Speed is 0.25h-1, reaction end obtains first order reaction product;
(2) described first order reaction product is sent into the top of the second reactor of 8L, and described first order reaction is produced
Gaseous component in thing is flowed out by second reactor top, and the solid-liquid component in first order reaction product flows downward,
Flow speed control is that the hydrogen counter current contacting flowed up in 1-10cm/s, with described second reactor is reacted, hydrogen oil
Ratio is 800, and reaction pressure is 17MPa, and bottom hydrogen dividing potential drop is 14MPa, and reaction temperature is 450 DEG C, air speed
For 0.30h-1, reaction obtains secondary response product after terminating;
(3) after the solid-liquid component fractionation in described secondary response product, liquid distillate and residue are obtained;By institute
State after the gaseous component in secondary response product mixes mutually with the gaseous component in first order reaction product and separate,
Obtain gas products and light distillate, wherein, the hydrogen-rich gas obtained can reuse anti-to A reactor and two grades
Answer in device and use as hydrogen.
Comparative example
The coal liquefaction using Chinese patent literature CN102115674A to be provided is made with petroleum refining combined method
For comparative example, select ub-bituminous coal coal dust as coal sample, 105 DEG C, be dried 30 points under the protection of high pure nitrogen
Clock is standby.
At a temperature of 95 DEG C, according to coal dust 200g, petroleum distillate I 120g, product liquid fraction I 180g's
Proportional arrangement coal, wherein the boiling range of petroleum distillate I is 150-343 DEG C, from catalytic cracking unit, through adding
After hydrogen processes, hydrogenation of aromatics content is 60%, and the boiling range of product liquid fraction I is 180-490 DEG C, hydrotreating
Rear hydrogenation of aromatics content is 70%.Adding the active component of 0.4wt% in coal is ferrum, the urging of molybdenum element
Agent (wherein molybdenum is 0.05 with the atomic ratio of ferrum), then inserts the first order reaction of 10L together with the Cosan of 1g
In device, boost after being passed through hydrogen exchange air, start to warm up not after reactor pressure is raised to 8.5MPa
Disconnected stirring, reaches constant temperature 30min after reaction temperature 400 DEG C;Backward first reactor effluent in add stone
Oil distillate II (selected from catalytic cracking unit) 70g, product liquid fraction II 50g are also together sent into 8L's by bottom
In second reactor, it is warmed up to constant temperature 60min after reaction temperature 450 DEG C.The boiling range of petroleum distillate II is
343-520 DEG C, the boiling range of product liquid fraction II is 360-550 DEG C.
Reaction terminate after cool down reactor to room temperature, reactor pressure reduces to draw off during normal pressure mixture in still,
Metering, sampling is made simulated distillation analysis, is calculated each fraction quality.
In above-described embodiment and comparative example, coal charge used, heavy oil and slag oil properties see table 1.
Table 1
Pulverized bituminous coal | Ub-bituminous coal coal dust | |
Moisture/wt% | 5.1 | 4.88 |
Ash/wt% | 7.3 | 8.88 |
Volatile matter/wt% | 40.31 | 34.67 |
Sulfur content/wt% | 0.8 | 0.58 |
Nitrogen content/wt% | 2.13 | 1.15 |
Oxygen content/wt% | 14 | 11 |
Particle diameter/um | 50 | 60 |
Heavy oil | Residual oil | |
Density (20 DEG C)/kg m-3 | 916.2 | 956.3 |
Condensation point/DEG C | 12 | 20 |
Kinematic viscosity (80 DEG C)/mm s-1 | 46.8 | 56.3 |
Sulfur/% | 0.51 | 2.1 |
Total metal/ppm | 120 | 196 |
Coal dust treatment effeciency in embodiment of the present invention 1-6 and comparative example technique and finally give each gas fraction,
The yield of liquid distillate and residue see table 2.
Table 2
As seen from Table 2, at embodiment of the present invention 1-6 and each gas fraction of comparative example, liquid
Body fraction and residue yield are essentially identical, and embodiment of the present invention 1-6 and comparative example employ identical one-level
In the case of reactor, second reactor carry out two-stage hydrogenation DCL/Direct coal liquefaction reaction, the coal dust of embodiment 1-6
Treatment effeciency is compared comparative example and is doubled, and illustrates to use two-stage of the present invention hydrogenation direct coal liquefaction process
Production efficiency can be significantly improved, be significant hence for DCL/Direct coal liquefaction industry.
Although the present invention has carried out detailed elaboration by above-mentioned specific embodiment to it, but, this specialty
Those of ordinary skill should be understood that any shape without departing from claims made on this basis
Formula and the change of details, belong to invention which is intended to be protected.
Claims (10)
1. a direct coal liquefaction process for two-stage hydrogenation, comprises the steps,
(1) coal dust and hydrogen supply solvent being mixed into coal slurry, described coal slurry, hydrogen and catalyst react, instead in A reactor
Answering temperature to be 420-460 DEG C, reaction end obtains first order reaction product;
(2) described first order reaction product is sent into the top of second reactor, and the gaseous component in described first order reaction product is by two grades
Reactor head flows out, and solid-liquid component flows downward in described second reactor, flows up in described second reactor
Hydrogen counter current contacting is reacted, and reaction temperature is 430-480 DEG C, and reaction obtains secondary response product after terminating;
(3) by the solid-liquid Component seperation in described secondary response product.
Technique the most according to claim 1, it is characterised in that in described second reactor, described solid-liquid component flows downward
Flow velocity be 1-10cm/s.
Technique the most according to claim 1 and 2, it is characterised in that the hydrogen-oil ratio 600-1000 in described second reactor.
Technique the most according to claim 1 and 2, it is characterised in that the hydrogen dividing potential drop in described second reactor is 10-15MPa.
Technique the most according to claim 1 and 2, it is characterised in that the reaction pressure in described second reactor is 15-
20MPa。
Technique the most according to claim 1 and 2, it is characterised in that in described A reactor, reaction pressure is 15-
20MPa, hydrogen dividing potential drop is 10-15MPa.
Technique the most according to claim 1 and 2, it is characterised in that the coal dust content of described coal slurry is 30-50wt%, described
The weight of catalyst is the 0.1-10.0% of described coal dust weight.
Technique the most according to claim 1 and 2, it is characterised in that described coal dust is the one in bituminous coal and ub-bituminous coal or two
Kind, described hydrogen supply solvent is the mixture of one or more in heavy oil, residual oil and step (3) in liquid distillate.
Technique the most according to claim 1 and 2, it is characterised in that in step (1), by described coal slurry, catalyst and hydrogen
Gas mixing, pressurize and heat after, bottom send in described A reactor.
Technique the most according to claim 1 and 2, it is characterised in that the gaseous component in described secondary response product and one-level
Gaseous component in product separates after mixing mutually, and isolated hydrogen-rich gas is as the hydrogen in step (1) and (2)
Gas uses.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310385008.XA CN104419439B (en) | 2013-08-29 | 2013-08-29 | A kind of direct coal liquefaction process of two-stage hydrogenation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201310385008.XA CN104419439B (en) | 2013-08-29 | 2013-08-29 | A kind of direct coal liquefaction process of two-stage hydrogenation |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104419439A CN104419439A (en) | 2015-03-18 |
CN104419439B true CN104419439B (en) | 2016-08-17 |
Family
ID=52969569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201310385008.XA Active CN104419439B (en) | 2013-08-29 | 2013-08-29 | A kind of direct coal liquefaction process of two-stage hydrogenation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN104419439B (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104560098B (en) * | 2014-11-27 | 2016-09-07 | 波露明(北京)科技有限公司 | A kind of coal direct liquefaction method |
CN107163974A (en) * | 2017-06-21 | 2017-09-15 | 华东理工大学 | A kind of multistage supplies the direct coal liquefaction process method of hydrogen supply dissolvent |
CN109957416A (en) * | 2017-12-22 | 2019-07-02 | 何巨堂 | With the hydrocarbon material process for selective hydrogenation of liquid material product circulation formula counter-current reactor |
CN110373228A (en) * | 2019-06-27 | 2019-10-25 | 中国石油大学(华东) | A kind of coal heavy oil two stage hydro coprocessing process |
CN110551515B (en) * | 2019-10-17 | 2021-12-28 | 胜帮科技股份有限公司 | Device and method for preparing aromatic hydrocarbon through coal staged hydropyrolysis |
CN111876189B (en) * | 2020-07-21 | 2022-09-02 | 中国神华煤制油化工有限公司 | Method for two-stage catalytic direct liquefaction of coal and application thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4189375A (en) * | 1978-12-13 | 1980-02-19 | Gulf Oil Corporation | Coal liquefaction process utilizing selective heat addition |
US4495055A (en) * | 1982-04-05 | 1985-01-22 | Hri, Inc. | Coal catalytic hydrogenation process using direct coal slurry feed to reactor with controlled mixing conditions |
US4510037A (en) * | 1983-12-23 | 1985-04-09 | Hri, Inc. | Hydrogenation process for solid carbonaceous feed materials using thermal countercurrent flow reaction zone |
JPS61101592A (en) * | 1984-10-24 | 1986-05-20 | Nippon Kokan Kk <Nkk> | Direct liquefaction of coal |
CN1189538C (en) * | 2000-09-28 | 2005-02-16 | 碳氢技术股份有限公司 | Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material |
CN1243813C (en) * | 2003-02-14 | 2006-03-01 | 煤炭科学研究总院北京煤化学研究所 | Coal directly-liquifying process with series counter-current and circulating coal-liquifying reactor |
CN1869159A (en) * | 2006-06-27 | 2006-11-29 | 神华集团有限责任公司 | Method of directly liquifying coal |
CN101028586A (en) * | 2007-01-29 | 2007-09-05 | 煤炭科学研究总院 | Multi-phase bubbling reactor |
CN102482580A (en) * | 2009-08-19 | 2012-05-30 | Ifp新能源公司 | Direct coal liquefaction with integrated product hydrotreating and catalyst cascading |
-
2013
- 2013-08-29 CN CN201310385008.XA patent/CN104419439B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4189375A (en) * | 1978-12-13 | 1980-02-19 | Gulf Oil Corporation | Coal liquefaction process utilizing selective heat addition |
US4495055A (en) * | 1982-04-05 | 1985-01-22 | Hri, Inc. | Coal catalytic hydrogenation process using direct coal slurry feed to reactor with controlled mixing conditions |
US4510037A (en) * | 1983-12-23 | 1985-04-09 | Hri, Inc. | Hydrogenation process for solid carbonaceous feed materials using thermal countercurrent flow reaction zone |
JPS61101592A (en) * | 1984-10-24 | 1986-05-20 | Nippon Kokan Kk <Nkk> | Direct liquefaction of coal |
CN1189538C (en) * | 2000-09-28 | 2005-02-16 | 碳氢技术股份有限公司 | Hydro inversion catalyzing multi-stage method, and refining hydrocarbon raw material |
CN1243813C (en) * | 2003-02-14 | 2006-03-01 | 煤炭科学研究总院北京煤化学研究所 | Coal directly-liquifying process with series counter-current and circulating coal-liquifying reactor |
CN1869159A (en) * | 2006-06-27 | 2006-11-29 | 神华集团有限责任公司 | Method of directly liquifying coal |
CN101028586A (en) * | 2007-01-29 | 2007-09-05 | 煤炭科学研究总院 | Multi-phase bubbling reactor |
CN102482580A (en) * | 2009-08-19 | 2012-05-30 | Ifp新能源公司 | Direct coal liquefaction with integrated product hydrotreating and catalyst cascading |
Also Published As
Publication number | Publication date |
---|---|
CN104419439A (en) | 2015-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104419439B (en) | A kind of direct coal liquefaction process of two-stage hydrogenation | |
CN106635157B (en) | A kind of lightening method of inferior feedstock oil | |
CN105567321A (en) | Method for producing oil product by corefining coal and oil | |
CN104962307B (en) | Method for producing light oil through coal liquefaction | |
RU2010123026A (en) | ADDITIVE FOR THE HYDROPROCESSING PROCESS AND METHOD FOR PRODUCING AND USING IT | |
CN105001900A (en) | Technology of synthesizing gasoline by coke oven gas through methyl alcohol | |
CN105462610A (en) | Anthracene oil hydrogenation method | |
CN107267186A (en) | The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon | |
US10508247B2 (en) | Process of maximizing production of chemical raw materials by gaseous phase catalytic cracking crude oil with multi-stages in milliseconds in combination with hydrogenation | |
CN102234531B (en) | Device for catalytically cracking heavy oil in sections and application thereof | |
CN202912908U (en) | Heavy oil thermal cracking and gasification coupled double reaction tube circulating bed device | |
CN104449836B (en) | The trans hydrocracking process of a kind of full cut of coal tar | |
CN106281449A (en) | A kind of coal tar produces light Fuel and the method and system of needle coke | |
US2194574A (en) | Process for producing gasoline and gas | |
WO2014110085A1 (en) | Direct coal liquefaction process | |
CN106221792A (en) | A kind of anthracene oil hydrogenation method | |
CN112391197B (en) | Suspension bed residual oil hydrocracking system and method | |
CN106635160B (en) | A kind of coal and coal tar mixed hydrogenation system and technique | |
CN104419436B (en) | A kind of direct coal liquefaction process using poor oil | |
CN104419438B (en) | A kind of direct coal liquefaction process being mixed with middle coalite tar | |
CN105754648B (en) | Coal tar processing method and its system | |
CN104560098B (en) | A kind of coal direct liquefaction method | |
CN104419437B (en) | A kind of direct coal liquefaction process that is mixed with high temperature coal-tar | |
CN109401784B (en) | Comprehensive utilization method of heavy inferior oil and oil shale | |
CN108148624B (en) | Short-flow circulation method for solvent oil used in reaction process of directly preparing oil by coal hydrogenation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant |